Polymer hetero-electrolyte enabled solid-state 2.4-V Zn/Li hybrid batteries.

The high redox potential of Zn0/2+ leads to low voltage of Zn batteries and therefore low energy density, plaguing deployment of Zn batteries in many energy-demanding applications. Though employing high-voltage cathode like spinel LiNi0.5Mn1.5O4 can increase the voltages of Zn batteries, Zn2+ ions will be immobilized in LiNi0.5Mn1.5O4 once intercalated, resulting in irreversibility. Here, we design a polymer hetero-electrolyte consisting of an anode layer with Zn2+ ions as charge carriers and a cathode layer that blocks the Zn2+ ion shuttle, which allows separated Zn and Li reversibility. As such, the Zn‖LNMO cell exhibits up to 2.4 V discharge voltage and 450 stable cycles with high reversible capacity, which are also attained in a scale-up pouch cell. The pouch cell shows a low self-discharge after resting for 28 days. The designed electrolyte paves the way to develop high-voltage Zn batteries based on reversible lithiated cathodes.

Modular Design of Functional Glucose Monomer and Block Co-Polymer toward Stable Zn Anodes.

Aqueous Zn batteries employing mildly acidic electrolytes have emerged as promising contenders for safe and cost-effective energy storage solutions. Nevertheless, the intrinsic reversibility of the Zn anode becomes a focal concern due to the involvement of acidic electrolyte, which triggers Zn corrosion and facilitates the deposition of insulating byproducts. Moreover, the unregulated growth of Zn over cycling amplifies the risk of internal short-circuiting, primarily induced by the formation of Zn dendrites. In this study, a class of glucose-derived monomers and a block copolymer are synthesized through a building-block assembly strategy, ultimately leading to uncover the optimal polymer structure that suppresses the Zn corrosion while allowing efficient ion conduction with a substantial contribution from cation transport. Leveraging these advancements, remarkable enhancements are achieved in the realm of Zn reversibility, exemplified by a spectrum of performance metrics, including robust cycling stability without voltage overshoot and short-circuiting during 3000 h of cycling, stable operation at a high depth of charge/discharge of 75% and a high current density, >95% Coulombic efficiency over 2000 cycles, successful translation of the anode improvement to full cell performance. These polymer designs offer a transformative path based on the modular synthesis of polymeric coatings toward highly reversible Zn anode.

Bio-Inspired Dynamically Morphing Microelectronics toward High-Density Energy Applications and Intelligent Biomedical Implants.

Choreographing the adaptive shapes of patterned surfaces to exhibit designable mechanical interactions with their environment remains an intricate challenge. Here, a novel category of strain-engineered dynamic-shape materials, empowering diverse multi-dimensional shape modulations that are combined to form fine-grained adaptive microarchitectures is introduced. Using micro-origami tessellation technology, heterogeneous materials are provided with strategic creases featuring stimuli-responsive micro-hinges that morph precisely upon chemical and electrical cues. Freestanding multifaceted foldable packages, auxetic mesosurfaces, and morphable cages are three of the forms demonstrated herein of these complex 4-dimensional (4D) metamaterials. These systems are integrated in dual proof-of-concept bioelectronic demonstrations: a soft foldable supercapacitor enhancing its power density (≈108 mW cm-2), and a bio-adaptive device with a dynamic shape that may enable novel smart-implant technologies. This work demonstrates that intelligent material systems are now ready to support ultra-flexible 4D microelectronics, which can impart autonomy to devices culminating in the tangible realization of microelectronic morphogenesis.

A Photolithographable Electrolyte for Deeply Rechargeable Zn Microbatteries in On-Chip Devices.

Zn batteries show promise for microscale applications due to their compatibility with air fabrication but face challenges like dendrite growth and chemical corrosion, especially at the microscale. Despite previous attempts in electrolyte engineering, achieving successful patterning of electrolyte microscale devices has remained challenging. Here, successful patterning using photolithography is enabled by incorporating caffeine into a UV-crosslinked polyacrylamide hydrogel electrolyte. Caffeine passivates the Zn anode, preventing chemical corrosion, while its coordination with Zn2+ ions forms a Zn2+-conducting complex that transforms into ZnCO3 and 2ZnCO3·3Zn(OH)2 over cycling. The resulting Zn-rich interphase product significantly enhances Zn reversibility. In on-chip microbatteries, the resulting solid-electrolyte interphase allows the Zn||MnO2 full cell to cycle for over 700 cycles with an 80% depth of discharge. Integrating the photolithographable electrolyte into multilayer microfabrication creates a microbattery with a 3D Swiss-roll structure that occupies a footprint of 0.136 mm2. This tiny microbattery retains 75% of its capacity (350 µAh cm-2) for 200 cycles at a remarkable 90% depth of discharge. The findings offer a promising solution for enhancing the performance of Zn microbatteries, particularly for on-chip microscale devices, and have significant implications for the advancement of autonomous microscale devices.

Microelectronic Morphogenesis: Smart Materials with Electronics Assembling into Artificial Organisms.

Microelectronic morphogenesis is the creation and maintenance of complex functional structures by microelectronic information within shape-changing materials. Only recently has in-built information technology begun to be used to reshape materials and their functions in three dimensions to form smart microdevices and microrobots. Electronic information that controls morphology is inheritable like its biological counterpart, genetic information, and is set to open new vistas of technology leading to artificial organisms when coupled with modular design and self-assembly that can make reversible microscopic electrical connections. Three core capabilities of cells in organisms, self-maintenance (homeostatic metabolism utilizing free energy), self-containment (distinguishing self from nonself), and self-reproduction (cell division with inherited properties), once well out of reach for technology, are now within the grasp of information-directed materials. Construction-aware electronics can be used to proof-read and initiate game-changing error correction in microelectronic self-assembly. Furthermore, noncontact communication and electronically supported learning enable one to implement guided self-assembly and enhance functionality. Here, the fundamental breakthroughs that have opened the pathway to this prospective path are reviewed, the extent and way in which the core properties of life can be addressed are analyzed, and the potential and indeed necessity of such technology for sustainable high technology in society is discussed.

MXene and Carbon-Based Electrodes of Thermocells for Continuous Thermal Energy Harvest.

Low-grade heat represents a significant form of energy loss; thermocells (TECs) utilizing the thermogalvanic effect can convert thermal energy into electricity without generating vibrations, noise, or waste emissions, making them a promising energy conversion technology for efficiently harvesting low-grade heat. Despite recent advancements, the reliance on high-cost platinum electrodes in TECs has considerably hindered their widespread adoption. Developing cost-effective electrodes that maintain the same thermoelectrochemical performance is crucial for the successful application of TECs. In this review article, the exploration of MXene materials as TEC electrodes is discussed first, emphasizing the immense potential of the MXene family for low-grade heat harvesting applications. Next, recent research on carbon-based electrodes is summarized, and morphological and structural optimizations are comprehensively discussed aiming at enhancing the thermoelectrochemical performance of TECs. In the concluding section, the challenges are outlined and future perspectives are offered, which provide valuable insights into the ongoing development of high-performance TEC electrodes using MXene and carbon-based materials.

Zn Microbatteries Explore Ways for Integrations in Intelligent Systems.

As intelligent microsystems develop, many revolutionary applications, such as the swallowing surgeon proposed by Richard Feynman, are about to evolve. Nonetheless, integrable energy storage satisfying the demand for autonomous operations has emerged as a major obstacle to the deployment of intelligent microsystems. A reason for the lagging development of integrable batteries is the challenge of miniaturization through microfabrication procedures. Lithium batteries, generated by the most successful battery chemistry, are not stable in the air, thus creating major manufacturing challenges. Other cations (Na+ , Mg2+ , Al3+ , K+ ) are still in the early stages of development. In contrast, the superior stability of zinc batteries in the air brings high compatibility to microfabrication protocols and has already demonstrated excellent practicability in full-sized devices. To obtain energy-dense and high-power zinc microbatteries within square-millimeter or smaller footprints, sandwich, pillar, and Swiss-roll configurations are developed. Thin interdigital and fiber microbatteries find their applications being integrated into wearable devices and electronic skin. It is foreseeable that zinc microbatteries will find their way into highly integrated microsystems unlocking their full potential for autonomous operation. This review summarizes the material development, configuration innovation, and application-oriented integration of zinc microbatteries.

Ultra-dense plasmonic nanogap arrays for reorientable molecular fluorescence enhancement and spectrum reshaping.

Understanding interactions between molecular transition and intense electromagnetic fields confined by plasmon nanostructures is of great significance due to their huge potential in fundamental cavity quantum electrodynamics and practical applications. Here, we report reorientable plasmon-enhanced fluorescence leveraging the flexibilities in densely-packed gold nanogap arrays by template-assisted depositions. By finely adjusting the symmetry of the unit structure, arrays of nanogaps along two nearly-orthogonal axes can be tailored collectively with spacing down to sub-10 nm on a single chip, facilitating distinct "inter-cell" and "intra-cell" plasmon couplings. Through engineering two sets of nanogaps, the varying hybridization-induced plasmonic bonding modes lead to adjustable splitting of the fluorescence emission peak with a width up to 81 nm and narrowing of linewidths up to a factor of 3. Besides, polarization anisotropy with a ratio up to 63% is obtained on the basis of spectrally separated local hotspots with discrepant oscillation directions. The developed plasmonic nanogap array is envisaged to provide a promising chip-scale, cost-effective platform for advancing fluorescence-based detection and emission technologies in both classical and quantum regimes.

Microbatteries with twin-Swiss-rolls redefine performance limits in the sub-square millimeter range.

To maintain the downscaling of microelectronic devices with footprints less than one square millimeter, next-generation microbatteries should occupy the same area and deliver adequate energy for running a new generation of multi-functional microautonomous systems. However, the current microbattery technology fails in accomplishing this task because the micrometer-sized electrodes are not compatible with on-chip integration protocols and technologies. To tackle this critical challenge, an on-chip Swiss-roll microelectrode architecture is employed that exploits the self-assembly of thin films into ultra-compact device architectures. A twin-Swiss-roll microelectrode on a chip occupies a footprint of 0.045 mm2 and delivers an energy density up to 458 µW h cm-2. After packaging, the footprint of a full cell increases to 0.11 mm2 with a high energy density of 181 µW h cm-2. The volumetric energy density excluding the chip thickness is 16.3 mW h cm-3. These results open opportunities for deploying microbatteries as energy and power sources to drive smart dust microelectronics and microautonomous systems.

An Anode-Free Zn-Graphite Battery.

The anode-free battery concept is proposed to pursue the aspiration of energy-dense, rechargeable metal batteries, but this has not been achieved with dual-ion batteries. Herein, the first anode-free Zn-graphite battery enabled by efficient Zn plating-stripping onto a silver-coated Cu substrate is demonstrated. The silver coating guides uniform Zn deposition without dendrite formation or side reaction over a wide range of electrolyte concentrations, enabling the construction of anode-free Zn cells. In addition, the graphite cathode operates efficiently under reversible bis(trifluoromethanesulfonyl)imide anion (TFSI- ) intercalation without anodic corrosion. An extra high-potential TFSI- intercalation plateau is recognized at 2.75 V, contributing to the high capacity of graphite cathode. Thanks to efficient Zn plating-stripping and TFSI- intercalation-deintercalation, an anode-free Zn-graphite dual-ion battery that exhibits impressive cycling stability with 82% capacity retention after 1000 cycles is constructed. At the same time, a specific energy of 79 Wh kg-1 based on the mass of cathode and electrolyte is achieved, which is over two times higher than conventional Zn-graphite batteries (<30 Wh kg-1 ).

Interfacial Chemistry Triggers Ultrafast Radiative Recombination in Metal Halide Perovskites.

Efficient radiative recombination is essential for perovskite luminescence, but the intrinsic radiative recombination rate as a basic material property is challenging to tailor. Here we report an interfacial chemistry strategy to dramatically increase the radiative recombination rate of perovskites. By coating aluminum oxide on the lead halide perovskite, lead-oxygen bonds are formed at the perovskite-oxide interface, producing the perovskite surface states with a large exciton binding energy and a high localized density of electronic state. The oxide-bonded perovskite exhibits a ≈500 fold enhanced photoluminescence with a ≈10 fold reduced lifetime, indicating an unprecedented ≈5000 fold increase in the radiative recombination rate. The enormously enhanced radiative recombination promises to significantly promote the perovskite optoelectronic performance.

Dual-Redox-Sites Enable Two-Dimensional Conjugated Metal-Organic Frameworks with Large Pseudocapacitance and Wide Potential Window.

Advanced supercapacitor electrodes require the development of materials with dense redox sites embedded into conductive and porous skeletons. Two-dimensional (2D) conjugated metal-organic frameworks (c-MOFs) are attractive supercapacitor electrode materials due to their high intrinsic electrical conductivities, large specific surface areas, and quasi-one-dimensional aligned pore arrays. However, the reported 2D c-MOFs still suffer from unsatisfying specific capacitances and narrow potential windows because large and redox-inactive building blocks lead to low redox-site densities of 2D c-MOFs. Herein, we demonstrate the dual-redox-site 2D c-MOFs with copper phthalocyanine building blocks linked by metal-bis(iminobenzosemiquinoid) (M2[CuPc(NH)8], M = Ni or Cu), which depict both large specific capacitances and wide potential windows. Experimental results accompanied by theoretical calculations verify that phthalocyanine monomers and metal-bis(iminobenzosemiquinoid) linkages serve as respective redox sites for pseudocapacitive cation (Na+) and anion (SO42-) storage, enabling the continuous Faradaic reactions of M2[CuPc(NH)8] occurring in a large potential window of -0.8 to 0.8 V vs Ag/AgCl (3 M KCl). The decent conductivity (0.8 S m-1) and high active-site density further endow the Ni2[CuPc(NH)8] with a remarkable specific capacitance (400 F g-1 at 0.5 A g-1) and excellent rate capability (183 F g-1 at 20 A g-1). Quasi-solid-state symmetric supercapacitors are further assembled to demonstrate the practical application of Ni2[CuPc(NH)8] electrode, which deliver a state-of-the-art energy density of 51.6 Wh kg-1 and a peak power density of 32.1 kW kg-1.

Imperceptible Supercapacitors with High Area-Specific Capacitance.

Imperceptible electronics will make next-generation healthcare and biomedical systems thinner, lighter, and more flexible. While other components are thoroughly investigated, imperceptible energy storage devices lag behind because the decrease of thickness impairs the area-specific energy density. Imperceptible supercapacitors with high area-specific capacitance based on reduced graphene oxide/polyaniline (RGO/PANI) composite electrodes and polyvinyl alcohol (PVA)/H2 SO4 gel electrolyte are reported. Two strategies to realize a supercapacitor with a total device thickness of 5 µm-including substrate, electrode, and electrolyte-and an area-specific capacitance of 36 mF cm-2 simultaneously are implemented. First, the void volume of the RGO/PANI electrodes through mechanical compression is reduced, which decreases the thickness by 83% while retaining 89% of the capacitance. Second, the PVA-to-H2 SO4 mass ratio is decreased to 1:4.5, which improves the ion conductivity by 5000% compared to the commonly used PVA/H2 SO4 gel. Both advantages enable a 2 µm-thick gel electrolyte for planar interdigital supercapacitors. The impressive electromechanical stability of the imperceptible supercapacitors by wrinkling the substrate to produce folds with radii of 6 µm or less is demonstrated. The supercapacitors will be meaningful energy storage modules for future self-powered imperceptible electronics.

A Patternable and In Situ Formed Polymeric Zinc Blanket for a Reversible Zinc Anode in a Skin-Mountable Microbattery.

Owing to their high safety and reversibility, aqueous microbatteries using zinc anodes and an acid electrolyte have emerged as promising candidates for wearable electronics. However, a critical limitation that prevents implementing zinc chemistry at the microscale lies in its spontaneous corrosion in an acidic electrolyte that causes a capacity loss of 40% after a ten-hour rest. Widespread anti-corrosion techniques, such as polymer coating, often retard the kinetics of zinc plating/stripping and lack spatial control at the microscale. Here, a polyimide coating that resolves this dilemma is reported. The coating prevents corrosion and hence reduces the capacity loss of a standby microbattery to 10%. The coordination of carbonyl oxygen in the polyimide with zinc ions builds up over cycling, creating a zinc blanket that minimizes the concentration gradient through the electrode/electrolyte interface and thus allows for fast kinetics and low plating/stripping overpotential. The polyimide's patternable feature energizes microbatteries in both aqueous and hydrogel electrolytes, delivering a supercapacitor-level rate performance and 400 stable cycles in the hydrogel electrolyte. Moreover, the microbattery is able to be attached to human skin and offers strong resistance to deformations, splashing, and external shock. The skin-mountable microbattery demonstrates an excellent combination of anti-corrosion, reversibility, and durability in wearables.

Flexible Surface-Enhanced Raman Scattering Chip: A Universal Platform for Real-Time Interfacial Molecular Analysis with Femtomolar Sensitivity.

We propose and demonstrate a flexible surface-enhanced Raman scattering (SERS) chip as a versatile platform for femtomolar detection and real-time interfacial molecule analysis. The flexible SERS chip is composed of a flexible and transparent membrane and embedded plasmonic dimers with ultrahigh particle density and ultrasmall dimer gap. The chip enables rapid identification for residuals on solid substrates with irregular surfaces or dissolved analytes in aqueous solution. The sensitivity for liquid-state measurement is down to 0.06 molecule per dimers for 10-14 mol·L-1 Rhodamine 6G molecule without molecule enrichment. Strong signal fluctuation and blinking are observed at this concentration, indicating that the detection limit is close to the single-molecule level. Meanwhile, the homogeneous liquid environment facilities accurate SERS quantification of analytes with a wide dynamic range. The synergy of flexibility and liquid-state measurement opens up avenues for the real-time study of chemical reactions. The reduction from p-nitrothiophenol (PNTP) to p-aminothiophenol (PATP) in the absence of the chemical reducing agents is observed at liquid interfaces by in situ SERS measurements, and the plasmon-induced hot electron is demonstrated to drive the catalytic reaction. We believe this robust and feasible approach is promising in extending the SERS technique as a general method for identifying interfacial molecular traces, tracking the evolution of heterogeneous reactions, elucidating the reaction mechanisms, and evaluating the environmental effects such as pH value and salty ions in SERS.

Stamping Fabrication of Flexible Planar Micro-Supercapacitors Using Porous Graphene Inks.

High performance, flexibility, safety, and robust integration for micro-supercapacitors (MSCs) are of immense interest for the urgent demand for miniaturized, smart energy-storage devices. However, repetitive photolithography processes in the fabrication of on-chip electronic components including various photoresists, masks, and toxic etchants are often not well-suited for industrial production. Here, a cost-effective stamping strategy is developed for scalable and rapid preparation of graphene-based planar MSCs. Combining stamps with desired shapes and highly conductive graphene inks, flexible MSCs with controlled structures are prepared on arbitrary substrates without any metal current collectors, additives, and polymer binders. The interdigitated MSC exhibits high areal capacitance up to 21.7 mF cm-2 at a current of 0.5 mA and a high power density of 6 mW cm-2 at an energy density of 5 µWh cm-2. Moreover, the MSCs show outstanding cycling performance and remarkable flexibility over 10 000 charge-discharge cycles and 300 bending cycles. In addition, the capacitance and output voltage of the MSCs are easily adjustable through interconnection with well-defined arrangements. The efficient, rapid manufacturing of the graphene-based interdigital MSCs with outstanding flexibility, shape diversity, and high areal capacitance shows great potential in wearable and portable electronics.

Decoding of Oxygen Network Distortion in a Layered High-Rate Anode by In Situ Investigation of a Single Microelectrode.

Sluggish conversion reactions severely impair the rate capability for lithium storage, which is the main disadvantage of the conversion-type anode materials. Here, the microplatform based on a single microelectrode is designed and utilized for the fundamental understanding of the conversion reaction. The kinetic-favorable layered structure of the anode material is on-site synthesized in the microplatform. The in situ characterization reveals that introducing an oxygen network distortion in the layered oxide anode effectively circumvents the severe passivation of the electrode material by lithium oxide, thus leading to highly reversible conversion reactions. As a result, the high-rate capability of the conversion-type anode materials is realized. The on-site synthesis strategy is further applied in the large-scale synthesis of nanomaterials for lithium-ion batteries. As such, oxide nanorods with the layered structure are synthesized by a facile chemical strategy, showing high rate performance (574 mAh g-1 at 10 A g-1). This work unveils the beneficial effect of oxygen network distortion in the layered anode for conversion reactions over cycling, thus providing an alternative strategy to enhance the rate capability of conversion-type anodes for lithium storage.

Stress-Actuated Spiral Microelectrode for High-Performance Lithium-Ion Microbatteries.

Miniaturization of batteries lags behind the success of modern electronic devices. Neither the device volume nor the energy density of microbatteries meets the requirement of microscale electronic devices. The main limitation for pushing the energy density of microbatteries arises from the low mass loading of active materials. However, merely pushing the mass loading through increased electrode thickness is accompanied by the long charge transfer pathway and inferior mechanical properties for long-term operation. Here, a new spiral microelectrode upon stress-actuation accomplishes high mass loading but short charge transfer pathways. At a small footprint area of around 1 mm2 , a 21-fold increase of the mass loading is achieved while featuring fast charge transfer at the nanoscale. The spiral microelectrode delivers a maximum area capacity of 1053 µAh cm-2 with a retention of 67% over 50 cycles. Moreover, the energy density of the cylinder microbattery using the spiral microelectrode as the anode reaches 12.6 mWh cm-3 at an ultrasmall volume of 3 mm3 . In terms of the device volume and energy density, the cylinder microbattery outperforms most of the current microbattery technologies, and hence provides a new strategy to develop high-performance microbatteries that can be integrated with miniaturized electronic devices.